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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,351 records · Page 75
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Improving Stability of Zeolites in Aqueous Phase via Selective Removal of Structural Defects

This work reports significant improvement in the hydrothermal stability of a well-characterized BEA zeolite via the selective removal of structural defects. Recent work suggests that the presence of silanol defects destabilizes the framework integrity of most zeolites and makes them susceptible to hydrolysis of the siloxy bonds by hot liquid water. The described approach allows for a key removal of silanols as shown with 29Si-MAS-NMR. Subsequently, the material stability in hot liquid water, measured by retention of its crystallinity with X-ray diffraction (XRD), is found to be superior to defective zeolites. In addition, N2-sorption measurements (BET) and transmission electron microscopy (TEM) show the formation of different types of mesoporosity for water-treated stabilized and unmodified materials. While the sorption capacity for untreated materials drops, related to re-precipitation of dissolved silica and pore blocking, the stabilized material retains its microporosity and improves its overall sorption capacity. The authors would like to thank B. W. Arey (PNNL) for HIM measurements and I. Arslan for TEM imaging. This work was supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. SP and MD acknowledge support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under Laboratory Directed Research & Development Program at PNNL.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2025

Defect-Driven Redox Interplay on Anatase TiO 2 : Surface-Structure Dependent Activation for CO 2 Hydrogenation Catalysis

Titanium dioxide (TiO 2 ) is one of the most extensively studied oxides as an active catalyst or catalyst support, particularly in energy and environmental applications, but the atomistic mechanisms governing its dynamic response to reactive environments and their correlation to reactivity remain largely elusive. Using in situ environmental transmission electron microscopy (ETEM), synchrotron X-ray diffraction (XRD), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), temperature-programmed reduction (TPR), reactivity measurements, and theoretical modeling, we reveal the dynamic interplay between oxygen loss and replenishment of anatase TiO 2 under varying reactive conditions. Under H 2 exposure, anatase TiO 2 undergoes surface reduction via lattice oxygen loss, forming Ti 3 O 5 . In contrast, CO 2 exposure induces oxygen replenishment, reversing stoichiometry. In mixed H2/CO 2 environments, the reverse water–gas shift (RWGS) reaction proceeds selectively on stepped and high-indexed TiO 2 surfaces, whereas the thermodynamically stable TiO 2 (101) surface remains inactive and intact. Critically, H 2 pretreatment generates oxygen vacancies on TiO 2 (101), transforming it into an active Ti 3 O 5 or defect-rich surface that catalyzes RWGS. By correlating surface structure, defect dynamics, and gas-phase interactions, this work deciphers the competition between H 2 -driven reduction and CO 2 -driven oxidation pathways at the atomic scale. Furthermore, these insights establish defect engineering as a strategic lever to activate inert TiO 2 facets, advancing the design of adaptive catalysts for sustainable fuel synthesis technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Stable Metal–Organic Electrocatalysts for Anion-Exchange Membrane Water Electrolyzers by Defect Engineering

Developing efficient and durable catalysts for the alkaline oxygen evolution reaction (OER) is vital to achieving practical anion-exchange membrane water electrolyzers (AEMWE) for green hydrogen production. In this work, we break the activity-stability trade-off of electrocatalysis by defect engineering of Ni-based metal-organic electrocatalysts (Ni-benzene dicarboxylate; Ni-BDC) through coordinating ferrocenecarboxylates (Fc) to the metal sites. Experimental results collectively reveal that the defect MOF (Ni-BDC:Fc_5:1) exhibits a high OER turnover frequency of 0.75 O 2 s -1 at 300 mV overpotential. Operando Raman spectroscopy and isotope-labelling electrochemical mass spectrometry measurements indicate the structure of Ni-BDC:Fc_5:1 is also more stable in service than that of pure Ni-BDC. The high activity and stability could be attributed to the moderate defects (i.e., unsaturated Ni sites) in the structure that not only increase the intrinsic activity and stability of the local active environment by inhibiting lattice oxygen exchange, but also electrochemically activates the bulk of the catalysts by creating a porous network that facilitates internal H 2 O/OH - conduction with enhanced electronic conduction. Accordingly, an AEMWE employing Ni-BDC:Fc_5:1 as the OER catalyst delivers an industrial-level current density of 1 A cm -2 at 1.73 V cell and can be steadily operated for more than 120 hours.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Understanding the Mechanism of Electronic Defect Suppression Enabled by Nonidealities in Atomic Layer Deposition

Silicon germanium (SiGe) is a multifunctional material considered for quantum computing, neuromorphic devices, and CMOS transistors. However, implementation of SiGe in nanoscale electronic devices necessitates suppression of surface states dominating the electronic properties. The absence of a stable and passive surface oxide for SiGe results in the formation of charge traps at the SiGe-oxide interface induced by GeOx. In an ideal ALD process in which oxide is grown layer by layer, the GeO x formation should be prevented with selective surface oxidation (i.e., formation of an SiO x interface) by controlling the oxidant dose in the first few ALD cycles of the oxide deposition on SiGe. However, in a real ALD process, the interface evolves during the entire ALD oxide deposition due to diffusion of reactant species through the gate oxide. In this work, this diffusion process in nonideal ALD is investigated and exploited: the diffusion through the oxide during ALD is utilized to passivate the interfacial defects by employing ozone as a secondary oxidant. Periodic ozone exposure during gate oxide ALD on SiGe is shown to reduce the integrated trap density (D it ) across the band gap by nearly 1 order of magnitude in Al 2 O 3 (<6 × 10 10 cm -2 ) and in HfO 2 (<3.9 × 10 11 cm -2 ) by forming a SiO x -rich interface on SiGe. Depletion of Ge from the interfacial layer (IL) by enhancement of volatile GeO x formation and consequent desorption from the SiGe with ozone insertion during the ALD growth process is confirmed by electron energy loss spectroscopy (STEM-EELS) and hypothesized to be the mechanism for reduction of the interfacial defects. In this work, the nanoscale mechanism for defect suppression at the SiGe-oxide interface is demonstrated, which is engineering of diffusion species in the ALD process due to facile diffusion of reactant species in nonideal ALD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Ionization-induced annealing of pre-existing defects in silicon carbide

A long-standing objective in materials research is to find innovative ways to remove preexisting damage and heal fabrication defects or environmentally induced defects in materials. Silicon carbide (SiC) is a fascinating wide-band gap semiconductor for high-temperature, high-power, high-frequency applications. Its high corrosion and radiation resistance makes it a key refractory/structural material with great potential for extremely harsh radiation environments. Here we show that the energy transferred to the electron system of SiC by energetic ions via inelastic ionization processes results in a highly localized thermal spike that can effectively heal preexisting defects and restore the structural order. This work reveals an innovative self-healing process using highly ionizing ions, and it describes a critical aspect to be considered in modeling SiC performance as either a functional or a structural material for device applications or high-radiation environments.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Planar defect-driven electrocatalysis of CO 2 -to-C 2 H 4 conversion

The selectivity towards a specific C 2+ product, such as ethylene (C 2 H 4 ), is sensitive to the surface structure of copper (Cu) catalysts in carbon dioxide (CO 2 ) electro-reduction. The fundamental understanding of such sensitivity can guide the development of advanced electrocatalysts, although it remains challenging at the atomic level. In this work, we demonstrated that planar defects, such as stacking faults, could drive the electrocatalysis of CO 2 -to-C 2 H 4 conversion with higher selectivity and productivity than Cu(100) facets in the intermediate potential region (–0.50 ~ –0.65 V vs. RHE). The unique right bipyramidal Cu nanocrystals containing a combination of (100) facets and a set of parallel planar defects delivered 67% faradaic efficiency (FE) for C 2 H 4 and a partial current density of 217 mA cm –2 at –0.63 V vs. RHE. In contrast, Cu nanocubes with exclusive (100) facets exhibited only 46% FE for C 2 H 4 and a partial current density of 87 mA cm –2 at an identical potential. Both ex situ CO temperature-programmed desorption and in situ Raman spectroscopy analysis implied that the stronger *CO adsorption on planar defect sites facilitates CO generation kinetics, which contributes to a higher surface coverage of *CO and in turn an enhanced reaction rate of C–C coupling towards C 2+ products, especially C 2 H 4 .

36 MATERIALS SCIENCE↗
DOE OSTI2015

Analysis of an optimization-based atomistic-to-continuum coupling method for point defects

Here, we formulate and analyze an optimization-based Atomistic-to-Continuum (AtC) coupling method for problems with point defects. Application of a potential-based atomistic model near the defect core enables accurate simulation of the defect. Away from the core, where site energies become nearly independent of the lattice position, the method switches to a more efficient continuum model. The two models are merged by minimizing the mismatch of their states on an overlap region, subject to the atomistic and continuum force balance equations acting independently in their domains. We prove that the optimization problem is well-posed and establish error estimates.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2014

The effect of defects and disorder on the electronic properties of ZnIr{sub 2}O{sub 4}

We analyze by means of ab initio calculations the role of imperfections on the electronic structure of ZnIr{sub 2}O{sub 4}, ranging from point defects in the spinel phase to the fully amorphous phase. We find that interstitial defects and anion vacancies in the spinel have large formation energies, in agreement with the trends observed in other spinels. In contrast, cation vacancies and antisites have lower formation energies. Among them, the zinc antisite and the zinc vacancy are the defects with the lowest formation energy. They are found to act as acceptors, and may be responsible for the spontaneous hole doping in the material. They may also induce optical transitions that would reduce the transparency of the material. Amorphization of ZnIr{sub 2}O{sub 4} leads a large decrease of the band gap and appearance of localized states at the edges of the band gap region, which may act as charge traps and prevent amorphous ZnIr{sub 2}O{sub 4} from being a good hole conductor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Point defect balance in epitaxial GaSb

Positron annihilation spectroscopy in both conventional and coincidence Doppler broadening mode is used for studying the effect of growth conditions on the point defect balance in GaSb:Bi epitaxial layers grown by molecular beam epitaxy. Positron annihilation characteristics in GaSb are also calculated using density functional theory and compared to experimental results. We conclude that while the main positron trapping defect in bulk samples is the Ga antisite, the Ga vacancy is the most prominent trap in the samples grown by molecular beam epitaxy. The results suggest that the p–type conductivity is caused by different defects in GaSb grown with different methods.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Point defects as a test ground for the local density approximation +U theory: Mn, Fe, and V{sub Ga} in GaN

Electronic structure of the Mn and Fe ions and of the gallium vacancy V{sub Ga} in GaN was analysed within the GGA + U approach. First, the +U term was treated as a free parameter, and applied to p(N), d(Mn), and d(Fe). The band gap of GaN is reproduced for U(N) ≈ 4 eV. The electronic structure of defect states was found to be more sensitive to the value of U than that of the bulk states. Both the magnitude and the sign of the U-induced energy shifts of levels depend on occupancies, and thus on the defect charge state. The energy shifts also depend on the hybridization between defect and host states, and thus are different for different level symmetries. In the case of V{sub Ga}, these effects lead to stabilization of spin polarization and the “negative-U{sub eff}” behavior. The values of Us were also calculated using the linear response approach, which gives U(Fe) ≈ U(Mn) ≈ 4 eV. This reproduces well the results of previous hybrid functionals calculations. However, the best agreement with the experimental data is obtained for vanishing or even negative U(Fe) and U(Mn)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Investigation of deep-level defects in Cu(In,Ga)Se{sub 2} thin films by a steady-state photocapacitance method

The properties of defect levels located 0.8 eV above the valence band in Cu(In{sub 1−x},Ga{sub x})Se{sub 2} thin films were investigated by a steady-state photocapacitance method. When illuminated by light with a photon energy of 0.8 eV at 60 K, a fast increase, followed by a slow increase, was observed in the photocapacitance transients of all samples. Upon being re-exposed, samples with a low bandgap energy showed a slow decrease in photocapacitance transients. These observations were interpreted using a configuration coordinate model assuming two states for the 0.8 eV defect: a stable state D and its metastable state D* with a large lattice relaxation. The difference in the evolution mechanisms of the photocapacitance transients was attributed to the difference in the optical transition of carriers between the two states of the 0.8 eV defect and the valence and conduction bands.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Defect states and charge trapping characteristics of HfO{sub 2} films for high performance nonvolatile memory applications

In this work, we present significant charge trapping memory effects of the metal-hafnium oxide-SiO{sub 2}-Si (MHOS) structure. The devices based on 800 °C annealed HfO{sub 2} film exhibit a large memory window of ∼5.1 V under ±10 V sweeping voltages and excellent charge retention properties with only small charge loss of ∼2.6% after more than 10{sup 4 }s retention. The outstanding memory characteristics are attributed to the high density of deep defect states in HfO{sub 2} films. We investigated the defect states in the HfO{sub 2} films by photoluminescence and photoluminescence excitation measurements and found that the defect states distributed in deep energy levels ranging from 1.1 eV to 2.9 eV below the conduction band. Our work provides further insights for the charge trapping mechanisms of the HfO{sub 2} based MHOS devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Inherent point defects at the thermal higher-Miller index (211)Si/SiO{sub 2} interface

Electron spin resonance (ESR) studies were carried out on the higher-Miller index (211)Si/SiO{sub 2} interface thermally grown in the temperature range T{sub ox} = 400–1066 °C to assess interface quality in terms of inherently incorporated point defects. This reveals the presence predominantly of two species of a P{sub b}-type interface defect (interfacial Si dangling bond), which, based on pertinent ESR parameters, is typified as P{sub b0}{sup (211)} variant, close to the P{sub b0} center observed in standard (100)Si/SiO{sub 2}—known as utmost detrimental interface trap. T{sub ox} ≳ 750 °C is required to minimize the P{sub b0}{sup (211)} defect density (∼4.2 × 10{sup 12 }cm{sup −2}; optimized interface). The data clearly reflect the non-elemental nature of the (211)Si face as an average of (100) and (111) surfaces. It is found that in oxidizing (211)Si at T{sub ox} ≳ 750 °C, the optimum Si/SiO{sub 2} interface quality is retained for the two constituent low-index (100) and (111) faces separately, indicating firm anticipating power for higher-index Si/SiO{sub 2} interfaces in general. It implies that, as a whole, the quality of a thermal higher-index Si/SiO{sub 2} interface can never surmount that of the low-index (100)Si/SiO{sub 2} structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Wave-particle dynamics of waveform and defect evolutions in undulated nonlinear self-excited dust acoustic waves

The wave-particle dynamics for the evolutions of defects and surrounding pitchfork type waveforms of a weakly disordered self-excited dust acoustic wave is experimentally investigated in an rf dusty plasma system. Particle trajectories are tracked and correlated with waveform evolution to construct an Eulerian-Lagrangian wave-particle dynamical picture. It is found that the local accumulation and depletion of particles in the wave crest and rear, respectively, determines the local crest speed, and the growth and decay of the local crest height, which in turn determine the waveform evolution. The local crest height and the focusing and defocusing of particle trajectories due to the transverse force fields from the tilted wave crest and the non-uniform crest height along the wave crest are the key factors to determine the above particle accumulation and depletion. It explains the observations such as the lower speed of smaller crests, the straightening of the leading front of the pitchfork waveform associated with the transverse motion of defect to the open side, and the vertical defect gliding in the wave frame through the detachment of the strongly kinked pitchfork branch followed by its reconnection with the trailing crest.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Atomically resolved structural determination of graphene and its point defects via extrapolation assisted phase retrieval

Previously reported crystalline structures obtained by an iterative phase retrieval reconstruction of their diffraction patterns seem to be free from displaying any irregularities or defects in the lattice, which appears to be unrealistic. We demonstrate here that the structure of a nanocrystal including its atomic defects can unambiguously be recovered from its diffraction pattern alone by applying a direct phase retrieval procedure not relying on prior information of the object shape. Individual point defects in the atomic lattice are clearly apparent. Conventional phase retrieval routines assume isotropic scattering. We show that when dealing with electrons, the quantitatively correct transmission function of the sample cannot be retrieved due to anisotropic, strong forward scattering specific to electrons. We summarize the conditions for this phase retrieval method and show that the diffraction pattern can be extrapolated beyond the original record to even reveal formerly not visible Bragg peaks. Such extrapolated wave field pattern leads to enhanced spatial resolution in the reconstruction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Defect state passivation at III-V oxide interfaces for complementary metal–oxide–semiconductor devices

The paper describes the reasons for the greater difficulty in the passivation of interface defects of III–V semiconductors like GaAs. These include the more complex reconstructions of the starting surface which already possess defect configurations, the possibility of injecting As antisites into the substrate which give rise to gap states, and the need to avoid As-As bonds and As dangling bonds which give rise to gap states. The nature of likely defect configurations in terms of their electronic structure is described. The benefits of diffusion barriers and surface nitridation are discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Effects of graphene defect on electronic structures of its interface with organic semiconductor

Electronic structures of copper hexadecafluorophthalocyanine (F{sub 16}CuPc)/graphene with different defect density were studied with ultra-violet photoelectron spectroscopy. We showed that the charge transfer interaction and charge flow direction can be interestingly tuned by controlling the defect density of graphene through time-controlled H{sub 2} plasma treatment. By increasing the treatment time of H{sub 2} plasma from 30 s to 5 min, both the interface surface dipole and the electron transporting barrier at F{sub 16}CuPc/graphene interface are significantly reduced from 0.86 to 0.56 eV and 0.71 to 0.29 eV, respectively. These results suggested that graphene's defect control is a simple approach for tuning electronic properties of organic/graphene interfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Defect induced structural and thermoelectric properties of Sb{sub 2}Te{sub 3} alloy

Structural and thermoelectric properties of metallic and semiconducting Sb{sub 2}Te{sub 3} are reported. X-Ray diffraction and Raman spectroscopy studies reveal that semiconducting sample has higher defect density. Nature and origin of possible defects are highlighted. Semiconducting Sb{sub 2}Te{sub 3} hosts larger numbers of defects, which act as scattering center and give rise to the increased value of resistivity, thermopower, and power factor. Thermopower data indicate p-type nature of the synthesized samples. It is evidenced that the surface states are often mixed with the bulk state, giving rise to metallicity in Sb{sub 2}Te{sub 3}. Role of different scattering mechanism on the thermoelectric property of Sb{sub 2}Te{sub 3} is discussed.

36 MATERIALS SCIENCE↗